Rational design of graphyne-based dual-atom site catalysts for CO oxidation

Zhang, Zhenwei; Zhang, Liang; Wang, Xiaoyang; Feng, Yuan Ping; Liu, Xiangwen; Sun, Wenming

doi:10.1007/s12274-022-4823-3

Cited by 20 publications

(11 citation statements)

References 66 publications

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“…134−136 In general, the XANES spectrum can disclose the spatial arrangement, valence state, and d-band occupancy of the probed atom based on the adsorption edge and the curve shape, whereas EXAFS provides the type of coordination atoms and coordination numbers of the probed atom, as well as the coordination bond distances. 137,138 With extreme care of unbiased curve simulations particularly aided by DFT calculations, 139,140 as well as the combination of other structure characterizations such as HAADF-STEM and XPS, XAS could provide useful information on the number of metal− metal bonds in low-nuclearity metal clusters as well as their bonding with the underlying support. Such atomic-level insight is vital for understanding the structure−activity relations, atom− atom synergies and stability of metal clusters.…”

Section: Haadf-stemmentioning

confidence: 99%

Atom-Precise Low-Nuclearity Cluster Catalysis: Opportunities and Challenges

2023

ACS Catal.

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Supported low-nuclearity cluster catalysts (LNCCs, for example, the number of metal atoms is 2 ≤ n ≤ 10), between single atoms and nanoclusters in size, possess not only maximum atom efficiency but also highly tunable structures, including nuclearity, composition, local chemical environment, and quantum electronic structures, holding great promise for advanced catalysis in terms of high activity, high selectivity, and high stability at low cost. In contrast to single-atom catalysts, LNCCs can provide multiple adsorption sites and initiate atom−atom synergies within clusters, offering great possibilities to remarkably boost the catalytic reactivity. The electronic structures and catalytic performance of LNCCs can be highly atom dependent. The synthesis of atom-precise LNCCs is vital for catalytic performance optimization and the understanding of structure−activity relationships but remains greatly challenging. This perspective first summarizes the atom-controlled synthetic strategies for atomprecise LNCCs, including size-selected cluster deposition, selected-multinuclear precursor grafting, and atomic layer deposition, and then discusses the state-of-the-art techniques for the statistical structural characterization of atom-precise LNCCs and their atomdependent catalytic properties. Therein, we emphasize the essential roles of prominent electronic and geometric effects as well as atom−atom synergies in the atom-by-atom controlled catalytic performance, particularly activity and stability. Finally, we discuss the opportunities and challenges of LNCCs in heterogeneous catalysis.

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Section: Haadf-stemmentioning

confidence: 99%

Atom-Precise Low-Nuclearity Cluster Catalysis: Opportunities and Challenges

2023

ACS Catal.

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“…The introduction of Ptn crowded the α-MoC surface thus contributed to eliminating excess surface oxygen species and further improved its stability. Besides, they found the unique CO activation and successive reforming pathway ( 13 C 16 O *' + *' → 13 C *' + 16 O *' , 2 13 C *' + 2 18 OH *' → 2 13 C 18 O + H2 + 2 * + 2 *' , 13 C *' + 2 18 OH *' → 13 C 18 O2 + H2 + 2 * + 2 *' ) to produce additional hydrogen by transient kinetic analysis using 13 C 16 O and H2 18 O as feeds (Fig. 9d).…”

Section: Water-gas Shift Reactionmentioning

confidence: 99%

“…However, different from the early development stage of SACs, it becomes harder for researchers to elevate the catalytic performance of SACs through aimless trials. In order to move further, researchers start to focus on the synergetic catalysts (like dual-atom site catalysts [8][9][10][11][12][13] , single atoms plus NPs 14 ), physical picture 15,16 and the electronic properties of the catalysts 17,18 . Among these, the underlying electronic states of active sites (i.e., supported single metal atoms) need to be comprehensively investigated because they are the direct adsorption sites for reactants and intermediates, the subtle change in microenvironment of which could exert an influence on the internal reactivity 16,19 .…”

Section: Introductionmentioning

confidence: 99%

Enhancing Heterogeneous Catalysis by Electronic Property Regulation of Single Atom Catalysts

Luo¹,

Wang²

2023

Acta Physico Chimica Sinica

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Past decades have witnessed the flourish of single atom catalysts (SACs) owing to their high atom-utilization efficiency and completely exposed active sites, which endows SACs with remarkably enhanced catalytic activities for various reactions. In the early development stage of SACs, researchers focus on the improvement of the catalytic performance of the catalysts, whereas the intrinsic catalytic reaction mechanism and the relationship between the electronic states of the metal sites and catalytic performance are usually ignored. Moreover, some sophisticated and complex structures, such as dualatom SACs, heteroatomic doped SACs, SACs with precise second coordination shell, and other synergetic catalysts containing SACs, were fabricated recently. The insight into electronic metal-support interaction (EMSI) aids the understanding of the catalytic mechanism and thus serves as a guide for the fabrication of heterogeneous catalysts. Notably, the uniform active sites and characteristic local coordination configuration of SACs provide excellent platforms to study EMSI and bridge the gap between homogeneous and heterogeneous catalysts, which will contribute to the understanding of structure-performance relationships and enhance the development of SACs and rational design of heterogeneous catalysts. EMSI is especially important in heterogeneous catalysis. Through the rational design of the local coordination environment of SACs, the electronic structure of active sites can be accurately regulated, which will shift their d-band centers. This significantly alters the adsorption capability of intermediates and influences the final catalytic performance of the catalysts. With the development of advanced operando characterization techniques, the evolution of configuration, electronic properties, and local coordination environment could be revealed, thus providing researchers with a clear picture of the intrinsic mechanism of the catalytic system. In addition, with the aid of theoretical calculations, catalyst screening will be considerably more convenient, which will significantly reduce the number of aimless trials. After the optimal structure is determined, researchers should devise precise fabrication methods to realize the configuration. Herein, we initially introduce the basic principles and effects of EMSI. The stabilization, electronic property regulation, and electron transfer tunneling effects of EMSI are the foundation of SACs synthesis and catalytic mechanism elucidation, of which the former requires strong coordination stabilization energies while the latter focuses on the electronic state evolution of the active sites. Subsequently, EMSI applications in several important heterogeneous catalysis processes, such as selective hydrogenation, alcohol oxidation, water-gas shift reaction, and hydroformylation, are reviewed. Finally, the review discusses the challenges and future prospects for the future development of EMSI on SACs.

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“…Based on DFT calculations, it was reported that γ-graphyne supported dual-atom Rh could improve CO oxidation activity. [67] Interestingly, two Rh atoms acted in different roles in the reaction: one structural and another functional, while substituting the structural Rh with Co or Cu could keep the reactivity and reduce the cost.…”

Section: Oxidation Reactionsmentioning

confidence: 99%

“…The enhancement was attributed to the synergistic effect between Pt and Pd atoms, which separately served as the active site for CO and NO adsorption, thus lowering the energy barrier. Based on DFT calculations, it was reported that γ‐graphyne supported dual‐atom Rh could improve CO oxidation activity [67] . Interestingly, two Rh atoms acted in different roles in the reaction: one structural and another functional, while substituting the structural Rh with Co or Cu could keep the reactivity and reduce the cost.…”

Section: Multifaceted Reactivity Of Dacsmentioning

confidence: 99%

Inter‐Metal Interaction of Dual‐Atom Catalysts in Heterogeneous Catalysis

Chen,

Lin,

Pan

et al. 2023

Angew Chem Int Ed

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Dual‐atom catalysts (DACs) have been a new frontier in heterogeneous catalysis due to their unique intrinsic properties. The synergy between dual atoms provides flexible active sites, promising to enhance performance and even catalyze more complex reactions. However, precisely regulating active site structure and uncovering dual‐atom metal interaction remain grand challenges. In this review, we clarify the significance of the inter‐metal interaction of DACs based on the understanding of active center structures. Three diatomic configurations are elaborated, including isolated dual single‐atom, N/O‐bridged dual‐atom, and direct dual‐metal bonding interaction. Subsequently, the up‐to‐date progress in heterogeneous oxidation reactions, hydrogenation/dehydrogenation reactions, electrocatalytic reactions, and photocatalytic reactions are summarized. The structure‐activity relationship between DACs and catalytic performance is then discussed at an atomic level. Finally, the challenges and future directions to engineer the structure of DACs are discussed. This review will offer new prospects for the rational design of efficient DACs toward heterogeneous catalysis.

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Rational design of graphyne-based dual-atom site catalysts for CO oxidation

Cited by 20 publications

References 66 publications

Atom-Precise Low-Nuclearity Cluster Catalysis: Opportunities and Challenges

Atom-Precise Low-Nuclearity Cluster Catalysis: Opportunities and Challenges

Enhancing Heterogeneous Catalysis by Electronic Property Regulation of Single Atom Catalysts

Inter‐Metal Interaction of Dual‐Atom Catalysts in Heterogeneous Catalysis

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